Polymerization product and process for producing the same



Patented Mar. 5, 1940 UNITED STATES PATENT OFFICE POLYMERIZATION PRODUCT AND PROGESS FOR PRODUCIN G THE SAME Frederick E. Frey and Robert D. Snow, Bartlesville, kla., and Louis E. Fitch, Jr., deceased, late of Bartlesville, .0kla., by First National Bank in Bartlesville, administrator; Bartiesville, 0kla., assignors to Phillips Petroleum Company, Bartlesville, Okla, a corporation of Delaware No Drawing. Application September 6, 1938. Serial No. 228,701

2 Claims. (cl. zoo- 93) This invention relates to the manufacture of new and useful products, generally of high molecular weight, or polymeric in nature, by caus ing sulfur dioxide to react with unsaturated compounds other than the olefin or conjugated diolefin hydrocarbons, and to processes by which such reactions can be made to take place A further object of the invention is to produce high molecular weight compounds containing sulfur dioxide and having incorporatedin the molecule, radicals such as the hydroxyl or carcrystalline compound. Mathews and Strange,

U. S. 1,196,259 (1916), react isoprene and other conjugated diolefins Witrl S02 in the presence of mention is made of the reaction of $02 with unsaturated compounds other than simple olefins and conjugated 'diolefins. Furthermore, since methods for the reaction of many of the simple olefinic hydrocarbons are still unknown, it does not necessarily follow from the previous disclosures that unsaturated compounds other than hydrocarbons would react with $02. We have found, however, that many compounds other than simple olefins and conjugated diolefin hydrocarbons react with S0: to form high molecular weight polymers of a resinous nature.

, tensile'strength.

We have reacted the following materials with sulfur dioxide:

The unsaturated halogen derivatives, vinyl.

chloride and allyl chloride react readily with liquid SO: in the presence of a catalyst or in light. The vinyl chloride forms a white solid which is insoluble in $02", but which can be molded by heat and pressure. The allyl chloride forms a water white, glassy product somewhat soluble in 80:. After molding by heat and pressure, the resin exhibits high mechanical strength. The unsaturated alcohol, allyl alcohol, reacts readily with S0; in the presence of catalyst or light. The solid resin obtained The unsaturated ether, allyl ethyl ether,'reacts readily with S0: in the presence of catalyst or light. The solid resinous product can be molded by heat and pressure.

The olefin oxides, or inner ethers, ethylene oxide and propylene oxide react relatively more slowly with S0. in the presence of catalyst or light at temperatures up to 40 C. but preferably at about 0 C. The products are viscous fluids useful as softening agents, plasticizers, and solvents.

Esters of acrylic acid react readily with S0: in the presence of light or catalyst to form products of desired properties. Ethyl acrylate reacts ,to

form a soft, rubbery product soluble in S0: and many organic solvents.

' When S0: is passed into an unsaturated amine compound such as allyl-amine, the first energetic reaction is evidently between the -NH:

group and the S02. If after this reaction is com-- plete, an excess of S02 is added and the mixture is exposed to light, a further reaction takes place, forming a compound of high molecular weight.

Diallyl, a diolefln not having conjugated double bonds and consequently not being capable of undergoing 1-4 addition of $02, was found to react rapidly with 802 to form a white insoluble diiiicultly fusible solid.

The unsaturated. aldehyde, acrolein, reacts slowly with S0: in the presence of light or catalyst. The reaction can best be carriedout at temperatures below atmospheric. The product is a solid insoluble in 802.

The unsaturated acids, acrylic, ailylacetic, and undecylenic react readily with S0; in the preshas a very high ence of a. catalyst. or light. The products are insoluble in the excess 80:. They are softer than the products obtained from olefinic hydrocarbons of the same number of carbon atoms, the product of undecylenic acid being very soft and pliable.

The acetylene derivatives, ethyl acetylene and phenyl acetylene, react with S02 in the presence of light or a catalyst.

The acetylene polymers, vinyl acetylene, di-,

vinyl acetylene, and polydivinylacetylene, react slowly in liquid 80.: in the light or in the presence of a catalyst to form an insoluble brown solid.

The furane derivative, furfuryl alcohol, reacts with S02 in the light or in the presence of a catalyst. A jet black solid material which is practically insoluble and can be molded only at high temperatures and pressures is formed.

Other compounds which we have converted to resins by reaction with S02 are: allyl cyanide, allyl isothiocyanate, allyl thiourea, and allyl urea.

Other materials which should react with S02 are: crotonyl alcohol, chloroprene, bromoprene, unsaturated vegetable oils such astung oil, and partially chlorinated oleflns such as thedichloride or diallyl.

Inmost cases we have found that the treatment of the unsaturated product to remove any absorbed oxygen and oxidation products prior to reaction is desirable.

Although the reaction involves approximately equimolecular proportions ch80: and unsaturated compound, the reaction product usually removes excess So: from the reaction phase in the absorbed or dissolved form. It is, therefore,

generally desirable to use more than the molecular equivalent of S02.

Any of the'catalysts for these reactions previously discovered and disclosed can be used, insofar as they are compatible with the unsaturated compound to be converted to resin.

Resinous products formed from mixtures of simple oleflnic hydrocarbons and other unsaturated compounds appear to have properties which are generally intermediate between those formed from the individual constituents.

In many ways the production of resins from such compounds as unsaturated halogen derivatives, alcohols, ethers, esters, acids and aldehydes, or materials containing them, by reaction with S0: is highly desirable and advantageous. It would permit the production of resins having special properties; for example the allyl alcohol- SO: resin hasunusually high tensile strength, while the undecylenic acid-S0: and ethyl acrylate-SO: resins are soft and rubbery. Then, too, a resin in which is tied up such a compound of multiple functions should be capable of further modification of properties by other chemicalreactions after formation of the SO: complex. Apparently only the carbon to carbon double bond is involved in the resin reaction, leaving the other functional groups, such as hydroxyl or carboxyl, more or less free to undergo its characteristic reactions. Thus, an allyl alcohol resin or an acrylic acid resin might be esterifled in the usual manner with acid anhydrides or alcohols, respectively, to produce resins with a wide. range of properties. Still another advantage of the use of these compounds is that they can be used to modify the properties of resins from unsaturated hydrocarbons and '80:. This may be accomplished in' either of two. ways; the unsaturated pol'yfunctional compound may bemixed with the amass unsaturated hydrocarbon and S02 before reaction, in which case opportunity is afforded for molecules of both types of unsaturated compounds to build into the same resin molecule; or the resins of the two types of compounds may be formed by reactingseparately with S02, and then be blended in the desired proportions after reaction.

We have produced useful resinous products by the reaction of $02 with unsaturated compounds other than simple olefinic hydrocarbons and conjugated dioleiinic hydrocarbons, have blended the resins so obtained with resins formed by the reaction of $02 with simple olefins and/or diolefins in order to modify the properties of the latter and have also mixed such unsaturated compounds with the simple oleflns and dioleflns and reacted the mixture with S02 under the proper conditions.

The following examples will illustrate the process of the present invention:

I. Equal volumes of liquid S02 and allyl chloride are sealed in a glass tube and exposed to sunlight or artificial light, preferably of short wave length. After the reaction has gone to com-' pletion, as indicated by the conversion of the fluid reactants to a stifi gel, the excess S02 is allowed to evaporate, leaving a white solid' resin.

As a variation of the above, suitable for'larger scale operation, the mixture of S02 and allyl chloride is placed in a bomb or autoclave provided with a suitable source of internal illumination and the reaction is promoted photochemically.

11. Equal volumes of liquid S02 and allyl alcohol are placed in a bomb or autoclave containing 0.01-0.l per cent of silvernitrate, or other H suitable catalyst and are allowed to react after thorough mixing. After the reaction has gone to completion, the excess S0: is allowed to escape and the solid resin is removed from the vessel.

III. To a mixture of 25 parts by weight of undecylenic acid and '75 parts of propylene was added somewhat more than twice its weight of liquid sulfur dioxide. solution consisting of 5% alcoholic lithium nitrate solution in ethyl alcohol was added at therate of 2 per cent of the weight'of the reaction mixture. The mixture was agitated while reaction was taking place. After completion of the reaction, the excess sulfur dioxide was removed. A

After mixing, a catalyst resin having much better plasticity than that. of propylene-sulfur dioxide resin was obtained.

elasticity than the product made from propylene alone.

Wemay also use other unsaturated acids and their esters. such as acrylic, allyl acetic, which. will'th'emselves react with sulfurdioxide in the absence of olefin hydrocarbons, in admixtures with olefin hydrocarbons. We prefer to use unsaturated acids or their esters in which the double bond is located at or near the end of the molecule opposite the carboxyl group and in which no branching of the hydrocarbonchain occurs at the double bond.

This application is based upon applicants Patent 2,114,292, issued April 19, 1938. The invention covered by the patent relates to the reaction of sulfur dioxide with vinyl and allyl chlorides whereas the invention claimed herein relates to the reaction of sulfur dioxide with diallyland the product produced thereby.

We claim:

1. The process of forming high molecular reacting S0: with diallyl.

2. As a new composition of matter, a high molecular weight heteropoiymeric product in the form of a white insoluble, difllcultly fusible solid containing diallyl and sulfur dioxide in chemical combination.

FIRST NATIONAL BANK IN BARTLESVILLE,

Administrator of the Estate of Louis H. Fitch, 

